Electroconductive resins and process of preparation

ABSTRACT

Electroconductive cationic resins prepared by the reaction of a 1,4-dihaloalkene-2 compound and a di(tertiary amine). The resins are quaternary ammonium compounds. They may be prepared in aqueous medium. They may be blended with polyvinyl alcohol and the blends may be used to provide solvent resistant electroconductive coatings to sheet materials used in electrographic printing.

This application is a continuation in part of application Ser. No.253,016, filed May 15, 1972 now U.S. Pat. No. 3,825,511 issued July 23,1974.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a sheet material for use in theelectrographic printing wherein the sheet material is prepared bytreatment with a water-soluble conductive substance. More particularly,it relates to sheet materials with electroconductive water-solublequaternary resin comprising at least one member of the group of polymershaving recurring units of the general formula: ##EQU1## wherein: 1. X isa halogen selected from the group consisting of chlorine and bromine;

2. A is a divalent radical selected from the group consisting of1,4-butene-2-yl and 1,4-cyclopentene-2-yl radicals optionallysubstituted with chloro, methyl or ethyl radicals;

3. N is a nitrogen atom;

4. R is a divalent radical selected from the group consisting ofphenylene, xylylene and saturated and unsaturated alkylene radicals of 2to 6 carbon atoms optionally substituted with methyl and hydroxylradicals;

5. Y is a radical selected from the group consisting of C₁ to C₄ alkyl,C₁ to C₄ hydroxyalkyl, and when R is an ethylene radical, methylene sothat the Y radicals form an ethylene bridge between the nitrogen atomsconnected by R;

6. z is a radical selected from the group consisting of C₁ to C₄ alkyl,C₁ to C₄ hydroxyalkyl, and when R is an ethylene radical, methylene sothat the Z radicals form an ethylene bridge between the nitrogen atomsconnected by R; and

7. The degree of polymerization of the resin is such that the resin hasan intrinsic viscosity of at least 0.05 in 2 percent aqueous sodiumchloride at 25°C.

2. The Prior Art

Electrographic printing processes require composite sheet materialscomprising an electrically insulating layer on an electricallyconductive layer. The electrically conductive layer should possess asurface resistivity of no more than about 1 × 10¹⁰ to 1 × 10⁸ ohms overa relative humidity range of about 25 to 80 percent in order to beuseful. During the printing process, the sheet material is grounded byplacing it on a grounded electrical conductor so that, in effect, thelower surface of the electrically insulating layer is grounded to theconductor on which the sheet material rests, through the electricallyconductive layer. The requirement of good electrical conductivity in theconductive layer is a source of major difficulty in securing uniformlysatisfactory performance with dielectric and photoconductivereproduction papers under different climatic conditions of humidity andtemperature. Much effort has been expended to develop a conductive sheetmaterial which will exhibit a high degree of electroconductivity undervarying environmental conditions of temperature, relative humidity,sheet moisture, etc., as well as under the varying operating conditionswhich are encountered from one copying process and machine to the next.

Various means have been described for increasing the conductivity ofsheet material which is used in dielectric and photoconductive printingprocesses. Such means, while representing valuable contributions to theart, have certain drawbacks which detract from their overall usefulness.These drawbacks include loss of conductivity under conditions of varyinghumidity, poor aging properties, poor hold-out against solvent basedresins used to coat the sheet material, migration of the conductivematerial in the sheet, difficulty of preparation, undesirable odors,etc.

Polyvinyl alcohol provides a particularly effective treatment forsolvent hold-out. Unfortunately, none of the presently availableelectroconductive resins is compatible with polyvinyl alcohol.Incompatibility is shown inter alia by a pronounced decrease inconductivity when the electroconductive resin is blended with thepolyvinyl alcohol and applied to the sheet material.

A definite need exists for a water-soluble conductive material fortreating sheet material used in dielectric and photoconductive printingprocesses which will maintain a high electroconductivity under widelyvarying conditions of temperature and humidity. A further need existsfor an electroconductive material which will be compatible withpolyvinyl alcohol and other paper-making additives. A further needexists for an easily prepared water-soluble electroconductive materialwhich can be used to treat sheet material used in dielectric andphotoconductive processes.

SUMMARY OF THE INVENTION

The above-mentioned needs in the prior art are fulfilled by the presentinvention which provides a new class of electroconductive resin fortreatment of sheet material to be used in dielectric and photoconductiveprinting processes. The class of resins contain recurring units of thegeneral formula: ##EQU2## wherein: 1. X is a halogen selected from thegroup consisting of chlorine and bromine;

2. A is a divalent radical selected from the group consisting of1,4-butene-2-yl and 1,4-cyclopentene-2-yl radicals optionallysubstituted with chloro, methyl or ethyl radicals;

3. N is a nitrogen atom;

4. R is a divalent radical selected from the group consisting ofphenylene, xylene and saturated and unsaturated alkylene radicals of twoto six carbon atoms optionally substituted with methyl and hydroxylradicals;

5. Y is a radical selected from the group consisting of C₁ to C₄ alkyl,C₁ to C₄ hydroxyalkyl, and when R is an ethylene radical, methylene sothat the Y radicals form an ethylene bridge between the nitrogen atomsconnected by R;

6. z is a radical selected from the group consisting of C₁ to C₄ alkyl,C₁ to C₄ hydroxyalkyl, and when R is an ethylene radical, methylene sothat the Z radicals form an ethylene bridge between the nitrogen atomsconnected by R; and

7. The resin D.P. is such that the resin has an intrinsic viscosity ofat least 0.05 in 2 percent aqueous sodium chloride at 25°C.

The molecular weight of the resins is such that the intrinsic viscositymeasured in two percent aqueous sodium chloride is at least 0.05.

The preparation of the resins is conveniently carried out in aqueous ororganic solvent medium by a one-step reaction to yield the conductiveresin without the concomitant formation of inorganic acid or inorganicsalt. The reactants comprise a 1,4-dihaloalkene-2 compound and adi(tertiary amine). The di(tertiary amine) may be replaced in part witha poly(tertiary amine) to effect molecular weight buildup and chainbranching of the resin.

The resins are applied as an aqueous or solvent solution or dispersionby conventional coating methods to the sheet material to give a weightratio of resin to sheet material in the range of 1:1 to 1:100. Theresins can be blended with polyvinyl alcohol and applied to the sheetmaterial to obtain solvent hold out without substantial loss inconductivity.

THE PREFERRED EMBODIMENTS

The electroconductive resins used in the present invention are preparedby reaction of a 1,4-dihaloalkene-2 with a di(tertiary amine) to form aquaternary ammonium polymer.

The 1,4-dihaloalkene-2 can be a linear alkene of four to six carbonsoptionally with methyl or chloro substituents, or a cyclopenteneoptionally with methyl or chloro substituents. Examples of such1,4-dihaloalkenes include 1,4-dichlorobutene-2; 1,4-dibromobutene-2;1,2,4-trichlorobutene-2, 1,4-dibromo-2-chlorobutene-2;1,4-dichloro-2-methylbutene-2; 1,4-dibromo-2-methylbutene-2;1,4-dichloropentene-2; 1,4-dibromopentene-2; 1,4-dibromopentene-2;1,4-dichlorohexene-2; 1,4-dibromohexene-2; 1,4-dichlorocyclopentene-2and 1,4-dibromocyclopentene-2. These 1,4-dihaloalkene-2 compounds areconveniently prepared by the thermodynamically controlled addition ofhalogen to the corresponding alkadiene. Preferred 1,4-dihaloalkene-2compounds include 1,4-dichlorobutene-2; 1,4-dibromobutene-2;1,4-dichloropentene-2; 1,4-dichlorohexene-2 and1,4-dichlorocyclopentene-2. A particularly preferred 1,4-dihaloalkene-2is 1,4-dichlorobutene-2.

The di(tertiary amines) have the general formula: ##EQU3## wherein Nrepresents nitrogen, R is a phenylene radical, a xylylene radical or adivalent saturated or unsaturated alkylene radical of 2 to 6 carbonatoms optionally substituted with methyl or hydroxyl substituents. Y isan alkyl radical of 1 to 4 carbon atoms or a hydroxyalkyl radical of 1to 4 carbon atoms, or a methylene radical when R is an ethylene radical,so that the Y radicals form an ethylene bridge between the nitrogenatoms, and Z is an alkyl radical of 1 to 4 carbon atoms, or ahydroxyalkyl radical of 1 to 4 carbon atoms, or a methylene radical whenR is an ethylene radical, so that the Z radicals form an ethylene bridgebetween the nitrogen atoms. Examples of such di(tertiary amines) includeN,N,N',N'-tetramethyl-ethylenediamine, N,N'-dimethyl piperazine,triethylenediamine, N,N,N',N'-tetrakis(hydroxyethyl)ethylene-diamine,1,3-bis(dimethylamino)-2-hydroxypropane, and N,N,N',N'-tetramethylp-xylylenediamine.

A convenient method of preparing di(tertiary amines) exists in thereaction of secondary amines with 1,4-dihaloalkene-2-compounds.Secondary amines of general formula R₁ R₂ NH are used, wherein R₁ and R₂are C₁ to C₄ alkyl and hydroxyalkyl radicals. The preferred secondaryamines include dimethylamine, diethylamine, diethanolamine andpiperidine. The reaction is exemplified by the following scheme:

    2R.sub.1 R.sub.2 NH+ClCH.sub.2 -- CH = CH--CH.sub.2 Cl ##EQU4## The di(tertiary amine) thus produced is then reacted with excess 1,4-dihaloalkene-2 compound to produce the quaternary ammonium resin.

When the reaction between 1,4-dihaloalkene-2 and di(tertiary amine) iscarried out in aqueous medium, it is preferred to use a water-solubledi(tertiary amine) such as N,N,N',N'-tetramethyl ethylenediamine,N,N'-dimethylpiperazine, triethylenediamine or1,3-bis(dimethylamino)-2-hydroxypropane.

In the preparation of the quaternary ammonium polymers of the presentinvention, a quantity of di(tertiary amine) is dissolved or dispersed ina solvent and the substantially equimolar amount of 1,4-dihaloalkene-2is added. Alternatively, a dispersion or solution of 1,4-dihaloalkene isprepared and the substantially equimolar amount of di(tertiary amine) isadded. Substantially equimolar amounts of the reactants are amountswhich upon reaction yield quaternary ammonium polymers which have anintrinsic viscosity of at least 0.05 in 2 percent aqueous sodiumchloride at 25°C. The reaction is carried out at atmospheric pressure ata temperature between 25° and 100°C. or in a pressure vessel attemperatures above 100°C. At the lower temperatures, the reaction tendsto be sluggish. At the higher temperatures, excessive color forms in thereaction medium. Consequently, it is preferred to carry out the reactionat a temperature in the range of 35° to 60°C. so that a reasonable rateof reaction is obtained without excessive color formation.

Any liquid which is not appreciably reactive to the dihaloalkene or thedi(tertiary amine) may be selected as the reaction medium. A dispersionor solution of quaternary ammonium polymer is formed by the reaction andthe dispersion or solution may be applied to a base sheet to render itelectroconductive. Alternatively, the quaternary ammonium polymer can berecovered by evaporation of the liquid reaction medium. It can then bedispersed or dissolved in water and applied to the base sheet. Thepreferred reaction medium is selected from the group consisting of waterand the alkanols containing one to three carbon atoms, such as methylalcohol, ethyl alcohol and propyl alcohol. Particularly preferred mediainclude water and water-alkanol solutions containing up to 30 weightpercent of a C₁ to C₃ alkanol, since they are relatively non-flammable,non-toxic and allow the electroconductive resin to be applied readily tocellulose sheet materials. When the reaction is carried out in suchaqueous media, the di(tertiary amine) is dissolved or dispersed in asufficient quantity of aqueous medium and the dihaloalkene whichpossesses low solubility in such aqueous media is added at a rate tomaintain the reaction medium at the desired temperature. Vigorousagitation aids dispersion and increases the rate of reaction. Stirringis continued after the dihaloalkene has been added, until the reactionis substantially complete as gauged by the disappearance of the secondphase or by the substantial consumption of the more volatiledihaloalkene-2. Usually, two to four hours at 35° to 60°C. issufficient.

Surprisingly, although the 1,4-dihaloalkene-2 compounds are readilyhydrolyzed by water to yield alkenediols, the hydrolysis reaction doesnot interfere appreciably with the reaction between the amine and1,4-dihaloalkene-2 since there is little impairment in molecular weightof the reaction product from aqueous medium compared with the reactionproduct from anhydrous alcohol medium. However, it is preferred to addthe dihaloalkene to the aqueous solution of di(tertiary amine) ratherthan to add the di(tertiary amine) to an aqueous dispersion ofdihaloalkene so that hydrolysis is minimized.

When reaction is carried out in alcohol solution, a one phase reactionmedium is obtained. Stirring is used to disperse the reactants as theyare added. The reaction rate, however, is much less dependent onstirring rate. The resin can be applied to a base sheet as an alcoholsolution or it can be recovered by evaporation of the solvent. It canthen be dissolved in water.

The quantities of reactants and solvent are selected to give a resincontent in the final solution in the range of 10 to 90 percent. At lowconcentrations, the molecular weight of the polymer produced by thisstep-wise reaction tends to be low particularly when the reaction iscarried out in water. At high concentrations, excessive viscosityimpedes stirring and mixing. Hence, it is preferred to carry out thereaction initially at high concentration with addition of water duringthe reaction so that the resin content in the final solution is in therange of 30 to 70 percent.

The di(tertiary amine) may be replaced in part or completely with apoly(tertiary amine) to yield products comprising resins ranging fromthose with a branched molecular structure to those with a highlycrosslinked network structure. The di(tertiary amine) can contain from 0to 10 parts by weight of poly(tertiary amine) per 100 parts ofdi(tertiary amine) to yield a quaternary polymer upon reaction with1,4-dihaloalkene-2 which is not so tightly crosslinked that it cannotform coherent coatings when it is applied to a substrate. As usedherein, the term "poly(tertiary amine)" means an amine containing morethan 2 tertiary amine groups per molecule. Preferred poly(tertiaryamines) include N-alkyl polyalkylene polyamines such asN,N,N',N",N"-pentamethyl diethylenetriamine and N,N,N',N",N"-pentamethyldihexylenetriamine, hexamethylene-tetramine,2,4,6-tris(dimethylaminomethyl) phenol, poly (N-methyl ethylenimine) andpoly(N-hydroxyethyl ethylenimine).

As set forth above, the intrinsic viscosity of the resin in a 2 percentaqueous solution of sodium choride is at least 0.05 and may be infinitewhen there is sufficient poly(tertiary amine) present in the di(tertiaryamine) to form an insoluble gel. Such gels can be applied as dispersionsto the substrate to form an electroconductive coating. However, it ispreferred to apply the quaternary resins of the present invention asaqueous solutions of viscosity in the range of 30 to 1,000 cps. andsuitable coating rheology is obtained with solutions in this viscosityrange when the intrinsic viscosity of the quaternary resin is in therange of 0.1 to 1.0 in 2 percent aqueous sodium chloride.

In the application of the electroconductive resin to the sheet material,the resin can be incorporated on or with the sheet material by coatings,dipping, brushing, calendering or other conventional means. Preferably,an aqueous solution or dispersion of the resin is applied as a coatingand thereafter the sheet material is dried in the usual way in an ovenor on calender rolls. The term "sheet material" or "paper " includescellulosic and synthetic fiber sheet material upon which images may berecorded.

The proportion of electroconductive polymer can be varied in amount from1 to 500 parts per 500 parts of sheet material depending on the basisweight of the sheet. Where the electroconductive resin is incorporatedwith the sheet material by coating, a coating weight up to 15 pounds per3,000 square feet of base sheet is employed. Preferably, the coatingweight is between 0.5 and 3.5 pounds per 3,000 square feet since below0.5 pounds, the conductivity is inadequate and above 3.5 pounds, littlefurther increase in conductivity is observed. The amount of polymer tobe incorporated with the sheet material can be varied by selection of asuitable molecular weight and concentration of the polymer in theaqueous solution. The polymer is preferably applied as a continuoussurface coating for optimum conductivity. The molecular weight must beadequate for formation of a coherent film. Such coherence is associatedwith an intrinsic viscosity of at least 0.05 in 2 percent sodiumchloride at 25°C.

In a preferred embodiment of the invention, the electroconductive resinis the adduct of 1,4-dichlorobutene-2 and triethylenediamine.Electroconductive sheet materials which incorporate this polymer adductexhibit an exceptionally stable conductivity over a wide range ofhumidity. Adducts of 1,4-dichlorobutene-2 and blends oftriethylenediamine and other di(tertiary amine) containing as little as10 weight percent of triethylenediamine also show stability ofconductivity over a wide range of humidity.

In another preferred embodiment of the invention, the electroconductiveresin is the adduct of 1,4-dichlorobutene-2 and1,3-bis(dimethylamino)-2-hydroxypropane. In this case, the low cost ofthe di(tertiary amine) contributes to an economical conductive treatmentof the sheet material.

In the preparation of electrographic printing papers such as dielectricpapers or photoconductive papers, it is conventional to apply a topcoatof an organic solution or dispersion of an insulating resin to theelectroconductive sheet material. The organic solution tends to sinkinto the electroconductive sheet material especially when theelectroconductive resin is present as a light coating so that thedielectric or charge retention properties of the topcoat are impaired.In order to prevent this, it is conventional to formulate theelectroconductive resin with a solvent hold-out resin so that theelectroconductive sheet material becomes non-absorbent to thesubsequently applied organic solution or dispersion, and alsonon-absorbent to the solvent of liquid toner systems. A preferredsolvent hold-out resin is poly(vinyl alcohol). The electroconductivequaternary ammonium polymers used hitherto have been characterized bytheir incompatibility with poly(vinyl alcohol). The incompatibility ismanifested by stringing and gelling when aqueous solutions of poly(vinylalcohol) and quaternary ammonium polymer in sufficiently highconcentration to provide adequate viscosity for coating applications arecombined, or by phase separation of the combined solutions so that anon-uniform film is deposited when the sheet material is coated with ablend of poly(vinyl alcohol) and quaternary ammonium polymer and theelectroconductive properties are substantially impaired. Surprisingly,the quaternary ammonium polymers of the present invention have beenfound to be exceptionally compatible with poly(vinyl alcohol). Blends ofaqueous solutions of the polymers of the present invention andpoly(vinyl alcohol) show no stringiness, gelling, or phase separationand the coatings of such blends applied to the sheet material provideadequate conductivity to the sheet for electrographic printingprocesses. Blends containing between 20 and 60 parts by weight ofpoly(vinyl alcohol) and between 40 and 80 parts by weight ofpoly(quaternary ammonium) resin are used for improved solvent hold out.The poly(vinyl alcohol) is the product of hydrolysis of poly(vinylacetate) and may contain residual unhydrolyzed vinyl acetate units inthe range of 1 weight percent to 40 weight percent. The weight averagemolecular weight of the poly(vinyl alcohol) may range from 2,000 to500,000.

The following examples are set forth in illustration of this inventionand should not be construed as limitations thereof. Unless otherwiseindicated, all parts and percentages are given in terms of parts byweight. Add-on is the increase in weight of a ream of paper by additionof resin and adjuncts and is expressed as pounds per 3,000 square feet.

PART A - PREPARATION OF RESINS EXAMPLE 1 Reaction Product of1,3-Bis(dimethylamino)-2-hydroxypropane and 1,4-Dichlorobutene-2

A reaction vessel, equipped with stirrer, reflux condenser, droppingfunnel and thermometer is charged with 308 parts1,3-bis(dimethylamino-2-hydroxypropane and 594 parts water. To thestirred solution, 263 parts of 1,3-dichlorobutene-2 is added over a 90minute period. The batch temperature is allowed to rise from 31° to51°C. during the addition.

Following the addition, the solution is warmed briefly to 76°C., thencooled to 25°C. and diluted with 101 parts of water. The solution isallowed to stand for 16 hours. It is then filtered through a bed ofactivated charcoal to give a clear, very pale yellow solution containing45.2 percent of resin. The viscosity is 300 cps. at 25°C. When thesolution is cast and dried, a continuous film of resin is obtained.

The resin is recovered from the solution by evaporation of the solvent.A yellow resinous mass is obtained. The intrinsic viscosity measured at25°C. in a 2 percent aqueous solution of sodium chloride is 0.095.

EXAMPLES 2 THROUGH 9

The procedure of Example 1 is used to produce a series ofelectroconductive resins. In each case, the 1,4-dihaloalkene-2 isreacted with the substantially equimolar amount of di(tertiary amine) ata temperature in the range of 30° to 60°C. The term "substantiallyequimolar" is used to indicate that slight departures from the exactequimolar proportions of reactants are permissible to compensate forminor amounts of impurities in the reactants, such departures beinglimited by the requirement that the intrinsic viscosity of the resinproduced measured in 2 percent sodium chloride solution at 25°C. be atleast 0.05.

                                      TABLE I                                     __________________________________________________________________________    PREPARATION OF ELECTROCONDUCTIVE RESINS                                       Example                                                                            1,4-Dihaloalkene-2                                                                           Di(tertiary amine)                                                                          Solvent                                                                            Resin Solution                         __________________________________________________________________________    2    1,4-dichlorobutene-2                                                                         triethylenediamine                                                                          H.sub.2 O                                                                          clear, viscous                         3    1,4-dibromobutene-2                                                                          N,N,N',N'-tetramethyl                                                                       H.sub.2 O                                                                          clear, viscous                                             ethylenediamine                                           4    1,4-dichlorocyclopentene-2                                                                   N,N'-dimethylpiperazine                                                                     H.sub.2 O                                                                          clear, viscous                         5    1,4-dichloropentene-2                                                                        N,N,N',N'-tetrakis                                                                          H.sub.2 O                                                                          clear, viscous                                             (hydroxyethyl)                                                                ethylene diamine                                          6    1,4-dichlorobutene-2                                                                         1,3-bis(dimethyl-                                                                           MeOH clear, viscous                                             amino)                                                                        2-hydroxypropane                                          7    1,4-dichloro-2-methyl-                                                                       N,N,N',N'-tetramethyl                                                                       MeOH clear, viscous                              butene-2       hexylenediamine                                           8    1,4-dichlorohexene-2                                                                         N,N,N',N'-tetrabutyl                                                                        MeOH clear, viscous                                             ethylenediamine                                           9    1,4-dichlorobutene-2                                                                         N,N,N',N'-tetramethyl                                                                       PrOH clear, viscous                                             para-xylylene diamine                                     __________________________________________________________________________

EXAMPLE 10

This Example is set forth to show the effect of a trifunctional amine onthe molecular weight of the resin produced by interaction of1,4-dichlorobutene-2 and 1,3-bis(dimethylamino)-2-hydroxypropanecontaining 2,4,6-tris(dimethylaminomethyl)-phenol.

139 Parts of 1,3-bis(dimethylamino)-2-hydroxypropane and 8.3 parts of2,4,6-tris(dimethylaminomethyl)-phenol are dissolved in 150 parts ofwater. 64 Parts of 1,4-dichlorobutene-2 are added at a constant rateover a period of 20 minutes. The temperature rises to 60°C. Cooling isapplied to the reaction and a further 63 parts of 1,4-dichlorobutene-2are added at a constant rate over a period of 20 minutes with thetemperature held below 45°C. Stirring is continued for 45 minutes. Anadditional 160 parts of water is added. A clear, yellow solution isobtained. The solids content is 46.3 per cent. The viscosity is 2,740cps at 25°C.

EXAMPLE 11

This Example is set forth to show the preparation of anelectroconductive resin by reaction of diethylamine and1,4-dichlorobutene-2.

292 Parts of diethylamine are dissolved in 200 parts of ethanol andchilled in an ice bath. 125 Parts of 1,4-dichlorobutene-2 in 125 partsof ethanol are added dropwise with stirring. The ice bath is removed. Asthe solution warms to room temperature, a precipitate of diethylaminehydrochloride forms. Stirring is continued overnight, after which thereaction is filtered and the filtrate is concentrated by evaporation.Vacuum distillation of the crude product gives the desired Et₂ NCH₂CH=CHCH₂ NEt₂ (picrate m. 164-167; lit. m. equals 154°-155°C.).

51 Parts of this amine are dissolved in ethanol and 32 parts of1,4-dichlorobutene-2 are added with stirring until a clear solutionforms. Ethanol is removed and the residue is dissolved in water andfiltered.

EXAMPLE 12

175 Parts of ##SPC1##

are prepared from piperidine and 1,4-dichlorobutene-2 by the sametechnique as in Example 11 above, and are dissolved in approximately 400parts of benzene. 98.5 Parts of 1,4-dichlorobutene-2 are added dropwise.The benzene solution is maintained at 50°C., whereupon a whiteprecipitate forms. After 18 hours at 50°C., the precipitate is filtered,washed with benzene, and dried. 210 Parts of a sticky white powder areobtained. The powder is dissolved in water.

PART B -- FORMULATION OF ELECTROCONDUCTIVE RESINS EXAMPLE 13

This Example is set forth to demonstrate the formulation of a solventhold-out composition containing electroconductive resin and poly(vinylalcohol).

Ten parts of a poly(vinyl alcohol) characterized by a 4 per cent aqueoussolution viscosity of 5 cps at 20°C. and by a residual vinyl acetatecontent of 20 per cent are dissolved in 48 parts of water. A solution of22.2 parts of a 45 per cent aqueous solution of an electroconductiveresin reaction product of 1,4-dichlorobutene-2 and1,3-bis(dimethylamino)-2-hydroxypropane, of 300 cps viscosity at 25°C.is prepared. The solution of electroconductive resin is added to thepoly(vinyl alcohol) solution with stirring. A clear stable solutioncontaining 25 per cent solids is obtained. No phase separation occursduring a period of more than one month.

EXAMPLES 14 AND 15

Following the procedure of Example 13, aqueous dispersions ofelectroconductive resin and hold-out resin are prepared.

Example 14 is obtained by blending the electroconductive resin ofExample 1 with Gelva Emulsion TS-30, a polyvinyl acetate emulsionproduced by Monsanto Company, of average particle size 0.5 microncontaining polymer of number average molecular weight in the range of40,000 to 80,000. The blend ratio is 1:1 at a solids content of 45 percent.

Example 15 is obtained by blending the electroconductive resin ofExample 2 with Penford Gum 260, a hydroxyethyl ether derivative of cornstarch of intermediate viscosity, produced by Penick and Ford Ltd. Inc.The blend ratio is 1:1 at a solids content of 25 per cent.

PART C - EVALUATION OF ELECTROCONDUCTIVE SHEET MATERIAL EXAMPLE 16

A series of experiments is carried out to determine the surfaceresistivity of electroconductive papers.

In each of the series of experiments, a sheet of bleached sulfite basepaper of basis weight 35 pounds per ream, sized on one side, is coatedon the wire or felt side with a layer of an aqueous solution ofelectroconductive resin, the concentration of which is adjusted to givea viscosity in the range of 50 to 500 cps and an add-on in the range of0.5 to 3.0 pounds per 3,000 square feet. Coating is effected with thewire wound rod appropriate to the desired add-on. The coating is driedon a drum drier at 75°C. for a period of 3 minutes. The coated paper isweighed to determine the add-on.

Test pieces are cut from the coated paper. They are conditioned in airfor at least 24 hours at 25°C. and the requisite relative humidity. Theyare tested for surface resistivity by a procedure substantially likethat described in Standard Methods of Test for Insulation Resistance ofElectrical Insulating Materials, ASTM designation D-257-66. A KeithleyModel 6105 Resistivity Adapter coupled with a Cenco High Voltage DCPower supply providing a regulated DC voltage accurate to ± 1 per centis used to determine the resistivity. The excitation voltage is 200volts. Paper samples are conditioned at the required humidity level forat least 24 hours before surface resistivities are determined. Duplicatedeterminations are made.

Solvent hold-out is determined by the tentative test procedure developedby Tappi CA1120 on paper conditioned at 50 per cent relative humidityand 72°F. for 24 hours. The two test solutions contain 4g. of CyanamidCalco Oil Blue W dye per liter, respectively, of toluene and Isopar G, asaturated hydrocarbon solvent supplied by Humble Oil Co.

                  TABLE II                                                        ______________________________________                                        SURFACE RESISTIVITIES OF ELECTROCONDUCTIVE PAPERS                             Resin  Add-on, pounds                                                         Example                                                                              per 3,000 square                                                                             Surface Resistivity, ohms                               No.    feet           20% RH     50% RH                                       ______________________________________                                        1      0.60           1.5 × 10.sup.9                                                                     --                                                  1.36           3.8 × 10.sup.8                                                                     --                                           2      1.35           1.6 × 10.sup.8                                                                     --                                                  1.52             --       1.2 × 10.sup.9                                1.97           2.1 × 10.sup.8                                                                     2.1 × 10.sup.8                                2.60           2.0 × 10.sup.8                                                                     2.0 × 10.sup.8                         10     2.22           7.4 × 10.sup.10                                                                    --                                           11     1.27           2.2 × 10.sup.12                                                                    2.6 × 10.sup.9                                1.79           1.9 × 10.sup.12                                                                    2.7 × 10.sup.9                         12     1.96           4.3 × 10.sup.12                                                                    7.1 × 10.sup.9                                2.30           2.4 × 10.sup.12                                                                    5.1 × 10.sup.9                         13     1.71           2.0 × 10.sup.10                                                                    1.5 × 10.sup.8                         14     2.58           7.5 × 10.sup.8                                                                     1.4 × 10.sup.8                         15     1.52           1.2 × 10.sup.9                                                                     --                                           ______________________________________                                    

Note the constancy of the surface resistivity over the relative humidityrange of 20 to 50 per cent of paper coated with the electroconductiveresin of Example 2 prepared by reaction of 1,4-dichlorobutene-2 andtriethylenediamine. Note also the comparatively low values of surfaceresistivity of papers coated with blends of electroconductive resin andhold-out resin of Examples 13, 14 and 15.

EXAMPLE 17

A series of experiments is carried out to determine the effectiveness ofthe electroconductive coatings for hold-out organic solvent. The resinsidentified in Table III are applied to Weyerhauser size pressed paperstock with the wire wound rod appropriate to the desired add-on. Aseries of coatings containing the resins of Examples 1 and 2, andformulated resins of Examples 1 and 2 containing equal amounts by weightof binder resins selected from the group consisting of poly(vinylalcohol), poly(vinyl acetate, and hydroxyethylated starch, are prepared.Solvent hold-out data expressed as per cent penetration into the coatedpapers by the standard Isopar G and toluene solutions of dye are givenin Table III.

                                      TABLE III                                   __________________________________________________________________________    SOLVENT HOLD-OUT OF ELECTROCONDUCTIVE COATINGS                                                         Penetration, %                                       Coating on Weyerhauser                                                                       Add-on, lbs.                                                                            Isopar G                                                                            Toluene                                        Size Pressed Paper Stock                                                                     per 3000 sq. ft.                                                                        Solution                                                                            Solution                                       __________________________________________________________________________    Resin Example 1                                                                              1.5       1     12                                                            1.7       0     7                                                             2.1       0     2                                              Resin Example 1, poly-                                                                       1.7       0     0                                              vinyl alcohol, 50:50                                                          Resin Example 1, poly-                                                                       2.3       12    8                                              vinyl acetate, 50:50                                                                         3.0       2     2                                              Resin Example 1, hydroxy-                                                                    2.3       2     6                                              ethylated starch, 50:50                                                       Resin Example 2                                                                              2.5       100   100                                            Resin Example 2, poly-                                                                       1.8       1     1                                              vinyl alcohol, 50:50                                                          __________________________________________________________________________

The poly(vinyl alcohol) of the coatings listed in Table III is Gelvatol20-30 poly(vinyl Ford of Monsanto Company. The poly(vinyl acetate) isGelva TS-30 poly(vinyl acetate) emulsion of Monsanto Company. Thehydroxyethylated starch is Penford Gum 280 of Penick and Fort Ltd.

The data show that the electroconductive resin of Example 1 is excellentin solvent hold-out by itself and when it is formulated with poly(vinylalcohol). The hold-out is slightly impaired by poly(vinyl acetate) andhydroxyethylated starch. The electroconductive resin of Example 2 ismuch inferior in solvent hold-out compared with the resin of Example 1.However, when it is formulated with poly(vinyl alcohol), it is equal inperformance to the resin of Example 1.

From the above examples, it is apparent that a class ofelectroconductive resins has been developed for the treatment of sheetmaterials to impart good electroconductive properties.

The materials of this invention can also be used with those materialscommonly used in the paper making industry such as pigments, opacifiers,fillers, extruders, dyes, sizes, etc. In view of the foregoing, itshould be obvious that many variations can be made in this inventionwithout departing from its scope.

What is claimed is:
 1. A resin composition comprising from 20 to 60parts by weight of a poly(vinyl alcohol) and from 40 to 80 parts byweight of a poly(quaternary ammonium) resin, wherein the poly(vinylalcohol) contains in the range of 1 to 40 weight percent of unhydrolyzedvinyl acetate units and has a weight average molecular weight in therange of 2000 to 500,000 and wherein the poly(quaternary ammonium) resincontains recurring units of: ##EQU5## wherein X is chlorine or bromineand A is a divalent radical selected from the group consisting of --CH₂--CH=CH--CH₂ --, ##EQU6## and ##EQU7## and wherein the degree ofpolymerization is such that the resin has an intrinsic viscosity of atleast 0.05 determined on a 2 percent aqueous sodium chloride solution at25°C.
 2. The resin composition of claim 1 wherein A is --CH₂--CH=CH--CH₂, ##EQU8## or ##EQU9##
 3. The resin composition of claim 1wherein A is --CH₂ --CH=CH--CH₂.
 4. The resin composition of claim 1wherein the poly(quaternary ammonium) resin is the substantiallyequimolar reaction product of triethylenediamine and at least one1,4-dihaloalkene-2 selected from the group consisting of 1,4-dibromo-and 1,4-dichloro substitution products of butene-2, pentene-2, hexene-2,2-methylbutene-2, 2-chlorobutene-2 and cyclopentene-2.
 5. The resincomposition of claim 1 wherein the 1,4-dihaloalkene-2 is1,4-dichlorobutene-2.
 6. The resin composition of claim 1 wherein thetriethylenediamine contains 10 parts by weight of poly(tertiary amine)selected from the group consisting of N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl dihexylenetriamine,hexamethylenetetramine, 2,4,6-tris(dimethylaminomethyl)phenol,poly(N-methyl ethylenimine) and poly(N-hydroxyethyl ethylenimine) per100 parts by weight of triethylenediamine.
 7. The resin composition ofclaim 1 wherein the intrinsic viscosity is in the range of 0.1 to 1.0.8. A resin composition comprising from 20 to 60 parts by weight of apoly(vinyl alcohol) and from 40 to 80 parts by weight of apoly(quaternary ammonium) resin, wherein the poly(vinyl alcohol)contains in the range of 1 to 40 weight percent of unhydrolyzed vinylacetate units and has a weight average molecular weight in the range of2000 to 500,000 and wherein the poly (quaternary ammonium) resincontains recurring units of: ##EQU10## wherein X is chlorine or bromineand A is a divalent radical selected from the group consisting of --CH₂--CH=CH--CH₂ --, ##EQU11## and ##EQU12## and wherein the degree ofpolymerization is such that the resin has an intrinsic viscosity of atleast 0.05 determined on a 2 percent aqueous sodium chloride solution at25°C.
 9. The resin composition of claim 1 wherein A is --CH₂--CH=CH--CH₂, ##EQU13## or ##EQU14##
 10. The resin composition of claim1 wherein A is --CH₂ --CH=CH--CH₂ --.
 11. The resin composition of claim1 wherein the poly (quaternary ammonium) resin is the substantiallyequimolar reaction product of 1,3-bis(dimethylamino)-2-hydroxypropaneand at least one 1,4-dihaloalkene-2 selected from the group consistingof 1,4-dibromo- and 1,4-dichloro substitution products of butene-2,pentene-2, hexene-2, 2-methylbutene-2, 2-chlorobutene-2 andcyclopentene-2.
 12. The resin composition of claim 1 wherein the1,4-dihaloalkene-2 is 1,4-dichlorobutene-2.
 13. The resin composition ofclaim 1 wherein the 1,3-bis(dimethylamino)-2-hydroxypropane contains 10parts by weight of poly(tertiary amine) selected from the groupconsisting of N,N,N',N",N"-pentamethyl diethylenetriamine,N,N,N',N",N"-pentamethyl dihexylenetriamine, hexamethylenetetramine,2,4,6-tris(dimethylaminomethyl) phenol poly(N-methyl ethylenimine) andpoly(N-hydroxyethyl ethylenimine) per 100 parts by weight oftriethylenediamine.
 14. The resin composition of claim 1 wherein theintrinsic viscosity is in the range of 0.1 to 1.0.